Extended Data Fig. 1: Development of optimized proximity-reactive FnFSYs for iVAC-mediated PD-L1 degradation-coupled antigen presentation.
From: Intratumoural vaccination via checkpoint degradation-coupled antigen presentation
a, Model reactions of mono- or di-fluoro phenyl sulfurofluoridates (FnPSFs) with imidazole informed optimization of FnFSYs. 1 mM FnPSF reacted with 100 mM imidazole under the same conditions, analysed by LC-MS (n = 3 independent replicates). b, Representative LC curves of model reactions after 4 h. c, Relative reactivity of FnPSF variants with imidazole compared to the original form (n = 3 independent replicates). d, Chemoenzymatic synthesis of FnFSYs: Tyrosine phenol lyase (TPL) enabled scalable production of fluoride-substituted tyrosines, creating two mono-fluoro and four di-fluoro FnFSYs through fluorosulfurylation. e, Crosslinking reactions between FnFSYs and imidazole: 1 mM FnFSY reacted with 100 mM imidazole in Tris buffer (pH = 8.0) at 37 °C for 4 h; conversion was analysed by LC-MS (n = 3 independent replicates). f, Representative LC curves of FnFSYs reacting with imidazole after 4 h. g, Relative reactivity of FnFSYs with imidazole compared to the original FSY (n = 3 independent replicates). Data are the mean ± s.d. Statistics: one-way ANOVA (c, g) with Tukey’s multiple comparisons test. NS: not significant.
